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CHEMICAL BONDING

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1 18 1A 8A 2 13 14 15 16 17 2A 3A 4A 5A 6A
1
18
1A
8A
2
13
14
15
16
17
2A
3A
4A
5A
6A
7A
1+1+
2+22+
3-
2-
1-
1+
2+2+
2-
1-
3
4
5
6
7
8
9
10
11
12
1+
2+
3+
4+
5+5+
3+
2+
3++
2+
2+
2+
2+
3+
2-
1-
1+
2+
3+
4+4+
5+5+
2-
1-
1+
2+
3+
2+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
Neutral Atom
Positive Ion
Negative Ion
Neg
Neg
by
DR. STEPHEN THOMPSON
MR. JOE STALEY

The contents of this module were developed under grant award # P116B-001338 from the Fund for the Improve- ment of Postsecondary Education (FIPSE), United States Department of Education. However, those contents do not necessarily represent the policy of FIPSE and the Department of Education, and you should not assume endorsement by the Federal government.

CHEMICAL BONDING CONTENTS

2 Electronegativity

3 Road Map

4 Types Of Bonding

5 Properties Controlled By Chemical Bond

6 Polar Bonds

7 Metallic Bonding

8 Intermolecular Forces

9 Ions: Counting Electrons And Protons

10 Ionic And Atomic Radii

11 Ions And Energy

12 Lithium Fluoride

13 Crystal Packing

14 Crystal Packing

15 Crystal Packing

16 Covalent H 2

17 Quantization

18 Bond Length And Strength

19 Strong And Weak Bonds

20 Strong And Weak Bonds

21 Covalent To Metallic

22 Electron Delocalization

CHEMICAL BONDING

ELECTRONEGATIVITY

HydrogenCHEMICAL BONDING ELECTRONEGATIVITY 1 Metals 18 Electronegativity 1A 8A Metalloids 2 13 14 15 16 17

CHEMICAL BONDING ELECTRONEGATIVITY Hydrogen 1 Metals 18 Electronegativity 1A 8A Metalloids 2 13 14 15 16
1 Metals 18 Electronegativity 1A 8A Metalloids 2 13 14 15 16 17 2.1 Nonmetals
1
Metals
18
Electronegativity
1A
8A
Metalloids
2
13
14
15
16
17
2.1
Nonmetals
0
2A
3A
4A
5A
6A
7A
H
He
Group 18
0.98
1.57
2.04
2.55
3.04
3.44
3.98
0
Li Be
B C
N O
F Ne
0.93
1.31
1.61
1.9
2.19
2.58
3.16
0
3
4
5
6
7
8
9
10
11
12
Na
Mg
Al
Si
P
S
Cl
Ar
0.82
1
1.36
1.54
1.63
1.66
1.55
1.83
1.88
1.91
1.9
1.65
1.81
2.01
2.18
2.55
2.96
0
K Ca
Sc
Ti
V Cr
Mn
Fe
Co
Ni
Cu
Zn
Ga
Ge
As
Se
Br
Kr
0.82
0.95
1.22
1.33
1.6
2.16
1.9
2.2
2.28
2.2
1.93
1.69
1.78
1.96
2.05
2.1
2.66
2.6
Rb
Sr
Y
Zr
Nb
Mo
Tc
Ru
Rh
Pd
Ag
Cd
In
Sn
Sb
Te
I
Xe
0.79
0.89
1.1
1.3
1.5
2.36
1.9
2.2
2.2
2.28
2.54
2
2.04
2.33
2.02
2
2.2
0
Cs
Ba
La
Hf
Ta
W
Re
Os
Ir
Pt
Au
Hg
Tl
Pb
Bi
Po
At
Rn
0.7
0.89
1.1
Fr
Ra
Ac
Rf
Ha
Sg
Ns
Hs
Mt
Ce
Pr
Nd
Pm
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Th
Pa
U
Np
Pu
Am
Cm
Bk
Cf
Es
Fm
Md
No
Lr

Electronegativity is the ability of an atom to attract shared electrons to itself. It is largely the difference between the electronegativities of two atoms which determines what kind of bond is formed between them.

2

What is the most electronegative element?

What is the least electronegative element (aside from the noble gases)?

What is the range of electronegativity for the metals? Metalloids? Nonmetals?

Why is the electronegativity of the noble gases listed as zero?

For an electron shared between hydrogen and chlorine, would you expect the electron to be closer to the hydrogen or the chlorine?

CHEMICAL BONDING

ROAD MAP

HydrogenCHEMICAL BONDING ROAD MAP Metals Metalloids Nonmetals Group 18 1A 2A 3A 4A 5A 6A 7A

MetalsCHEMICAL BONDING ROAD MAP Hydrogen Metalloids Nonmetals Group 18 1A 2A 3A 4A 5A 6A 7A

MetalloidsCHEMICAL BONDING ROAD MAP Hydrogen Metals Nonmetals Group 18 1A 2A 3A 4A 5A 6A 7A

NonmetalsCHEMICAL BONDING ROAD MAP Hydrogen Metals Metalloids Group 18 1A 2A 3A 4A 5A 6A 7A

Group 18BONDING ROAD MAP Hydrogen Metals Metalloids Nonmetals 1A 2A 3A 4A 5A 6A 7A 8A H

1A 2A

3A 4A 5A 6A 7A 8A

H He Li Be B C N O F Ne Na Mg Al Cl Ar
H
He
Li
Be
B
C
N
O
F
Ne
Na
Mg
Al
Cl
Ar
K
Ca
Sc
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
Ga
Br
Kr
Rb
Sr
Y
Zr
Nb
Mo
Tc
Ru Rh
Pd
Ag
Cd
In
I
Xe
Cs
Ba
La
Hf
Ta
W
Re
Os
Ir
Pt
Au
Hg
Tl
Pb
Bi
Po
At
Rn
Fr
Ra
Ac
Rf
Ha
Sg
Ns
Hs Mt
Ce
Pr
Nd
Pm
Sm
Eu Gd Tb
Dy
Ho
Er Tm
Yb
Lu
Th Pa
U
Np
Pu Am Cm Bk Cf Es
Fm Md No
Lr
Er Tm Yb Lu Th Pa U Np Pu Am Cm Bk Cf Es Fm Md
Er Tm Yb Lu Th Pa U Np Pu Am Cm Bk Cf Es Fm Md

Electronegativity

Groups 1 and 2 Metals NonMetals and H NonMetals and H NonMetals and H Other
Groups 1 and 2 Metals NonMetals and H NonMetals and H NonMetals and H Other
Groups 1 and 2 Metals NonMetals and H NonMetals and H NonMetals and H Other
Groups 1 and 2 Metals NonMetals and H

Groups 1 and 2 Metals

Groups 1 and 2 Metals NonMetals and H
Groups 1 and 2 Metals NonMetals and H

NonMetals and H

Groups 1 and 2 Metals NonMetals and H NonMetals and H NonMetals and H Other Metals
Groups 1 and 2 Metals NonMetals and H NonMetals and H NonMetals and H Other Metals
Groups 1 and 2 Metals NonMetals and H NonMetals and H NonMetals and H Other Metals
NonMetals and H NonMetals and H
NonMetals and H NonMetals and H

NonMetals and H

NonMetals and H NonMetals and H
NonMetals and H NonMetals and H

NonMetals and H

Metals NonMetals and H NonMetals and H NonMetals and H Other Metals NonMetals and H Non
Metals NonMetals and H NonMetals and H NonMetals and H Other Metals NonMetals and H Non
Metals NonMetals and H NonMetals and H NonMetals and H Other Metals NonMetals and H Non
Other Metals NonMetals and H

Other Metals

Other Metals NonMetals and H
Other Metals NonMetals and H

NonMetals and H

H NonMetals and H NonMetals and H Other Metals NonMetals and H Non Metalloids Metalloids Metals
H NonMetals and H NonMetals and H Other Metals NonMetals and H Non Metalloids Metalloids Metals
H NonMetals and H NonMetals and H Other Metals NonMetals and H Non Metalloids Metalloids Metals
Non Metalloids Metalloids
Non Metalloids Metalloids
Non Metalloids Metalloids
Non Metalloids Metalloids

Non Metalloids

Non Metalloids Metalloids

Metalloids

H NonMetals and H NonMetals and H Other Metals NonMetals and H Non Metalloids Metalloids Metals
H NonMetals and H NonMetals and H Other Metals NonMetals and H Non Metalloids Metalloids Metals
H NonMetals and H NonMetals and H Other Metals NonMetals and H Non Metalloids Metalloids Metals
Metals   Metals

Metals

 
Metals   Metals

Metals

Ionic

BondingMetalloids Metalloids Metals   Metals Ionic Covalent Bonding Polar Bonding Polar Bonding Metallic

Covalent

BondingMetalloids Metalloids Metals   Metals Ionic Bonding Covalent Polar Bonding Polar Bonding Metallic Bonding 3

Polar

BondingMetalloids Metalloids Metals   Metals Ionic Bonding Covalent Bonding Polar Polar Bonding Metallic Bonding 3

Polar

BondingMetalloids Metalloids Metals   Metals Ionic Bonding Covalent Bonding Polar Bonding Polar Metallic Bonding 3

Metallic

BondingMetalloids Metalloids Metals   Metals Ionic Bonding Covalent Bonding Polar Bonding Polar Bonding Metallic 3

3

CHEMICAL BONDING

TYPES OF BONDING

The different types of chemical bonding are determined by how the valence electrons are shared among the bonded atoms.

In IONIC BONDING the valence electrons are com-

pletely transferred from one atom to the other atom. Ionic bonds occur between metals and nonmetals when there is a large difference in electronegativity.

In COVALENT BONDING the valence electrons are shared as pairs between the bonded atoms. Pure covalent bonding only occurs when two nonmetal atoms of the same kind bind to each other. When two

different nonmetal atoms are bonded or a nonmetal and

a metal are bonded, then the bond is a mixture of cova-

lent and ionic bonding called polar covalent bonding.

In POLAR BONDING the electrons are shared but NOT equally. Many compounds have the characteris- tics of BOTH ionic and covalent bonding. Electronega- tivity differences determine the balance of character.

In METALLIC BONDING the valence electrons are shared among all of the atoms of the substance. Metallic bonding occurs when metals bond to either themselves or mixed with other metals in alloys.

Using the periodic table of electronegativities from the last page, write down examples of atom pairs which you would expect to form covalent bonds, polar covalent bonds and ionic bonds.

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form covalent bonds, polar covalent bonds and ionic bonds. 4 Valence Electron Cloud Ionic Bonding Filled

Valence Electron Cloud

covalent bonds and ionic bonds. 4 Valence Electron Cloud Ionic Bonding Filled electron shell core Covalent

Ionic Bonding

and ionic bonds. 4 Valence Electron Cloud Ionic Bonding Filled electron shell core Covalent Bonding Polar

Filled electron shell core

bonds. 4 Valence Electron Cloud Ionic Bonding Filled electron shell core Covalent Bonding Polar Bonding Metallic

Covalent Bonding

bonds. 4 Valence Electron Cloud Ionic Bonding Filled electron shell core Covalent Bonding Polar Bonding Metallic

Polar Bonding

bonds. 4 Valence Electron Cloud Ionic Bonding Filled electron shell core Covalent Bonding Polar Bonding Metallic

Metallic Bonding

CHEMICAL BONDING

PROPERTIES CONTROLLED BY CHEMICAL BOND

Chemical bonding determines the physical properties of substances. These properties are listed below for covalent, ionic and metallic bonding.

Covalent

Gas, liquid, or a soft solid.

Low melting point and low boiling point.

Insoluble in H 2 O Soluble in nonpolar solvents.

Nonconductor of heat and electricity.

Nonlustrous

Ionic

Crystalline solid. Very high melting point. Soluble in H 2 O. Insoluble in nonpolar solvents.
Crystalline solid.
Very high melting point.
Soluble in H 2 O.
Insoluble in nonpolar solvents.
Nonconductor of heat and electricity.
Conducts electricity in aqueous solutions.
Examples: NaCl, CaCO 3

Metallic

Malleable solid.

High melting point and boiling point.

Insoluble in H 2 O. Insoluble in nonpolar solvents.

Conducts heat and electricity. Lustrous

Examples: gold, copper

Using the list of properties on the left, try to assign as many of the common substances in your environ- ment to one of the types of bonding.

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in your environ- ment to one of the types of bonding. 5 List and describe some

List and describe some substances which do not seem to fit into any of the three types of bonding.

CHEMICAL BONDING

POLAR BONDS

Ionic and covalent bonds are two ideal types. Many bonds share characteristics of both ionic and covalent bonding. They are called polar covalent bonds and they tend to occur between atoms of mod- erately different electronegativities. In polar covalent bonds the electrons belong predomi- nantly to one type of atom while they are still partially shared by the other type, as illustrated in the following pictures of the valence electron densities.

Separated Atoms

Valence electron(s) Filled electron shell core
Valence electron(s)
Filled electron shell core

Ionic Bond

Polar Covalent Bond

Covalent Bond

In the picture above, the separated atoms look alike. If, in fact, they are the same kind of atom, which of the three bonds shown is possible? Why only that one? What other type of bonding is possible between identical atoms?

Using the chart of electronegativities, arrange the following compounds in an order from most ionic
Using the chart of electronegativities, arrange the following compounds in an order from most ionic

Using the chart of electronegativities, arrange the following compounds in an order from most ionic to most covalent:

Using the chart of electronegativities, arrange the following compounds in an order from most ionic to
Al 2 O 3 , CaCl 2 , NaF , O 2 , NaCl,
Al 2 O 3 , CaCl 2 , NaF , O 2 , NaCl,

Al 2 O 3 , CaCl 2 , NaF , O 2 , NaCl,

Al 2 O 3 , CaCl 2 , NaF , O 2 , NaCl,
following compounds in an order from most ionic to most covalent: Al 2 O 3 ,
following compounds in an order from most ionic to most covalent: Al 2 O 3 ,
following compounds in an order from most ionic to most covalent: Al 2 O 3 ,
following compounds in an order from most ionic to most covalent: Al 2 O 3 ,

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CHEMICAL BONDING

METALLIC BONDING

‘ELECTRON SEA’ MODEL FOR METALS Metals are formed from elements on the left hand side of the periodic table. Having generally low electroneg- ativity they tend to lose their valence electrons easily. When we have a macroscopic collection of the same or similar type of metallic atoms, the valence electrons are detached from the atoms but not held by any of the other atoms. In other words, these valence elec- trons are free from any particular atom and are only held collectively by the entire assemblage of atoms. In a metal the ion cores are held more or less at fixed places in an ordered, or crystal, lattice. The valence electrons are free to move about under applied stimu- lation, such as electric fields or heat.

applied stimu- lation, such as electric fields or heat. e - + + + - e
e - + + + - e - e - e - e + +
e -
+
+
+
-
e
-
e
-
e
-
e
+
+
+
-
e
e -
e -
+
+
+
-
e

1

Picture 1 presents a regular arrangement of the ion cores for a metal with a single valence electron per atom as well as a snapshot of the location of the freely moving valence electrons.

2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+
2+
2+
2+
2+
2+
2+
2+
2+
2+

2

Picture 2 shows a collection of ion cores for a metal with two valence electrons. Draw in the valence electrons. (Little circles are good enough.) HINT: Metals are neutral in charge.

What is the origin of electrical and thermal conductivity in sodium metal?

Why do metals exhibit a wide range of melt- ing points and hardness?

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CHEMICAL BONDING

INTERMOLECULAR FORCES

In addition to covalent, polar, ionic and metallic bond- ing there are intermolecular forces which contribute to the stability of things. These include dipole-dipole forces, hydrogen bonding and London dispersion forces.

DIPOLE-DIPOLE FORCES

Many molecules are electric dipoles, that is, they have net positive charge on one part of the molecule and net negative charge on another part. Since opposite charges attract and like charges repel, these molecules will tend to orient themselves so that there is the most attraction and the least repulsion.

Why is dipole-dipole interaction more important in liquids than in solids? Why is it more important in liquids than in gases? Can homonuclear diatomic molecules such as H 2 , O 2 and N 2 have dipole-dipole forces?

HYDROGEN BONDING A particularly strong and important variety of dipole- dipole interaction is called hydrogen bonding. A hydrogen atom on one molecule is attracted to a highly electronegative atom in another molecule. Hydrogen bonding is strong both because of the high polarity involved and because the small size of the hydrogen atom permits a close approach between it and the electronegative atom

Hydrogen bonding is particularly noted between wa- ter molecules, but from the description given above you should be able to deduce other substances in which hydrogen bonding occurs.

LONDON DISPERSION FORCES

Even nonpolar molecules have a random fluctuation of charge making the molecule temporarily polar. This then induces an opposite fluctuation in a neighboring molecules so that the two molecules have opposite charges on their near sides and attract each other.

opposite charges on their near sides and attract each other. DIPOLE-DIPOLE INTERACTION HYDROGEN BONDING HYDROGEN OXYGEN

DIPOLE-DIPOLE INTERACTION

near sides and attract each other. DIPOLE-DIPOLE INTERACTION HYDROGEN BONDING HYDROGEN OXYGEN WATER MOLECULE F-F F-F

HYDROGEN BONDING

HYDROGEN

OXYGEN
OXYGEN

WATER

MOLECULE

INTERACTION HYDROGEN BONDING HYDROGEN OXYGEN WATER MOLECULE F-F F-F quantumquantum eeffect or quantumum effecteffect

F-F

F-F

quantumquantum eeffect
quantumquantum eeffect

or

quantumum effecteffect
quantumum effecteffect
HYDROGEN BONDING HYDROGEN OXYGEN WATER MOLECULE F-F F-F quantumquantum eeffect or quantumum effecteffect induced induced 8

induced HYDROGEN BONDING HYDROGEN OXYGEN WATER MOLECULE F-F F-F quantumquantum eeffect or quantumum effecteffect induced 8 HYDROGEN BONDING HYDROGEN OXYGEN WATER MOLECULE F-F F-F quantumquantum eeffect or quantumum effecteffect induced 8

inducedHYDROGEN BONDING HYDROGEN OXYGEN WATER MOLECULE F-F F-F quantumquantum eeffect or quantumum effecteffect induced 8

HYDROGEN BONDING HYDROGEN OXYGEN WATER MOLECULE F-F F-F quantumquantum eeffect or quantumum effecteffect induced induced 8

8

HYDROGEN BONDING HYDROGEN OXYGEN WATER MOLECULE F-F F-F quantumquantum eeffect or quantumum effecteffect induced induced 8

CHEMICAL BONDING

IONS: COUNTING ELECTRONS AND PROTONS

NEUTRAL ATOMS

Neutral atoms have the same number of electrons as protons. In the picture below, the nuclear charge is represented by the gray circle marked 3+, for the 3 protons in the nucleus of lithium. Electrons are marked as horizontal dashes, one for each electron.

Li 3+ In the pictures below, draw in the number of elec- trons required to
Li
3+
In the pictures below, draw in the number of elec-
trons required to make the atom neutral and write the
element symbol in the box to the left of the atom.
8+
9+
11+
17+

9

POSITIVE IONS Positive ions have more protons than electrons. Since the number of protons an atom has is fixed in ordinary chemical reactions, positive ions are produced by removing electrons from the atoms.

Li+

3+
3+

In the pictures below draw in the number of electrons needed to make the ion named in the box.

Na+ Mg 2+
Na+
Mg 2+
11+11+
11+11+
12+12+
12+12+

NEGATIVE IONS Negative ions have more electrons than protons. Since the number of protons is unchanged from the neutral atom, negative ions are formed by the addition of electrons.

In the pictures below draw in the number of electrons needed to make the ion named in the box.

2- O - F
2-
O
-
F
8+
8+
9+
9+

CHEMICAL BONDING

ATOMIC AND IONIC RADII

Neutral AtomCHEMICAL BONDING ATOMIC AND IONIC RADII 1 2 3 4 5 6 7 Positive Ion Negative

1

2

3

4

5

6

7

Positive IonBONDING ATOMIC AND IONIC RADII Neutral Atom 1 2 3 4 5 6 7 Negative Ion

Negative Ion 1 18 1A 8A 2 13 14 15 16 17 2A 3A 4A
Negative Ion
1
18
1A
8A
2
13
14
15
16
17
2A
3A
4A
5A
6A
7A
1+1+
2+22+
3-
2-
1-
1+
2+2+
2-
1-
3
4
5
6
7
8
9
10
11
12
1+
2+
3+
4+
5+5+
3+
2+
3++
2+
2+
2+
2+
3+
2-
1-
1+
2+
3+
4+4+
5+5+
2-
1-
1+
2+
3+
2+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+

In this version of the periodic table the relative sizes of both neutral atoms and of their most common ions are shown, as well as the charges on their ions. The atoms are shown as black outline circles and the ionic diameters are colored blue for positive ions and red for negative ions.

Why are the positive ions smaller than their neutral atoms while the negative ions are larger than the neutral atoms?

Why do both ions and atoms tend to grow larger as we go down the periodic table?

What is the smallest atom? What atom has the smallest ion (too small to show on the table)? Find the largest atom and identify it on a standard periodic table.

What kind of ions do atoms with large electronegativi- ties tend to form?

10

What makes the atoms and ions in the middle of peri- ods 4, 5 and 6 so small? What makes the samarium atom so large?

Identify the two kinds of atom which appear about the same size as their ion and explain why this is so.

Why are the antimony and beryllium ions so small? Differentiate between the causes.

Why are the Lanthanide ions of such similar size?

How might you use the chart of atomic and ionic radii to explain the strengths of ionic bonding between various ions?

Compare the ionic and atomic radii table above with the chart of electronegativities and attempt to explain as many aspects of the sizes of atoms and ions in terms of electronegativity as possible.

CHEMICAL BONDING

IONS AND ENERGY

0 ↑ ↑↓ ENERGY
0
↑↓
ENERGY

0

Add Energy ↑ ↑↓
Add Energy
↑↓
- e Add More Energy 0 0 - e 0 ↑↓ ENERGY ENERGY
-
e
Add More Energy
0
0
-
e
0
↑↓
ENERGY
ENERGY

The diagrams above show the ground state of the lithium atom, followed by an excited state, followed by the lithium ion with the free electron. What is the charge of the lithium ion in the right hand drawing?

In the diagrams above, draw in the electrons as ar- rows which occupy the ground state orbitals of the sodium atom in the left hand picture. In the right hand picture draw in the orbitals and electrons of the sodium ion.

-

e

0 ↑↓ ↑↓ ↑↓
0
↑↓
↑↓
↑↓
↑↓ ↑↓
↑↓
↑↓
the sodium ion. - e 0 ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ 0 ↑↓ ↑↓ ↑ ↑↓

0

↑↓ ↑↓ ↑ ↑↓ ↑↓ ENERGY
↑↓
↑↓
↑↓
↑↓
ENERGY

+ Energy

The diagrams above show the ionization of fluorine. What is the charge of the fluoride ion?

e

-

0 0 ENERGY
0
0
ENERGY

In the diagrams above, draw in the electrons (arrows) for the chlorine atom on the left and for the chloride ion on the right. What is the charge of the chloride ion?

11

CHEMICAL BONDING

LITHIUM FLUORIDE

2Li (s) → 2Li (g)

It requires 155 kJ/mol to separate lithium atoms from their body centered cubic crystal structure.

atoms from their body centered cubic crystal structure. 2Li ( g ) → 2Li + (

2Li (g) → 2Li + (g) + 2e - (g)

It requires 520 kJ/mol to ionize lithium atoms.

F 2(g) → 2F (g)

It requires 80 kJ/mol to dissociate the difluoride molecule.

2F (g) + 2e - (g) → 2F - (g)

Ionization of the fluorine atom gives off 328 kJ/mol of energy.

2Li + (g) + 2F - (g) → 2Li + F - (s)

Combining the lithium and fluoride ions into their crystal gives off 1030 kJ/mol of energy.

↑ ↑↓ ↑↓ Li Li + +
↑↓
↑↓
Li
Li +
+
off 1030 kJ/mol of energy. ↑ ↑↓ ↑↓ Li Li + + + e - Add

+

e

-

kJ/mol of energy. ↑ ↑↓ ↑↓ Li Li + + + e - Add the energies

Add the energies which are associated with the process a making lithium fluoride crystal lithium crystal and difluoride molecules. Is the net reaction endothermic or exothermic?

- e ↑↓ ↑↓ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ F F -
-
e
↑↓
↑↓
↑↓
↑↓
↑↓
↑↓
↑↓
↑↓
↑↓
F
F -
+
Li +

12

CHEMICAL BONDING

CRYSTAL PACKING

CHEMICAL BONDING CRYSTAL PACKING 1 The picture at left shows seven spheres packed as close to-

1

The picture at left shows seven spheres packed as close to- gether as possible in the plane. This is called close packing. How many gray spheres touch the green sphere?

close packing. How many gray spheres touch the green sphere? 2 The picture above shows how

2

The picture above shows how close packing can fill, or tile , the plane. Notice the little triangles (with curved sides) that lie in between the spheres. Some of them point up and some of them point down. Compare the number of each kind of triangle.

point down. Compare the number of each kind of triangle. 3 4 5 Using circles, sketch

3

point down. Compare the number of each kind of triangle. 3 4 5 Using circles, sketch

4

point down. Compare the number of each kind of triangle. 3 4 5 Using circles, sketch

5

down. Compare the number of each kind of triangle. 3 4 5 Using circles, sketch in

Using circles, sketch in the box above another way to tile the plane.

Picture 3 is simply picture 2 looked at through an angle.

Picture 4 shows the spheres of picture 3 topped by another plane of spheres set to fit as closely as pos- sible into the lower plane. For clarity, the second plane is semitransparent green with a black outline.

Picture 5 shows the same planes of atoms as in pic- ture 4 but viewed from above. What proportion of the triangular spaces between the spheres of the lower (grey) plane are occupied by the second (green) plane of spheres?

13

CHEMICAL BONDING

CRYSTAL PACKING

Picture 6 shows the same two layers as picture 5 but two different sets of spaces between the green spheres of layer 2 are marked either red or blue. We can construct a third layer by placing spheres either in the blue spaces or the red spaces.

placing spheres either in the blue spaces or the red spaces. 6 Notice that the blue

6

Notice that the blue spaces lie directly above the grey spheres of layer 1. If we use these spaces for layer 3 then we get a two level repeating structure. If we name layer 1 A and Name layer 2 B then we can describe the structure as ABABAB This is called hexagonal close packing or hcp for short. Alternatively we can place the third layer of spheres in the red spaces. Then the third layer is differently located than either of the first two and is named C. We can describe this structure as ABCABC It is called cubic close packing or ccp.

structure as ABCABC It is called cubic close packing or ccp. 7 hcp 8 ccp 1
7 hcp 8 ccp
7
hcp
8
ccp

14

Why can we not use both the red and the blue spaces for placing the layer 3 spheres?

Using colored pencils, pens or crayons, draw circles representing the hcp structure in the box

Using colored pencils, pens or crayons, draw circles representing the hcp structure in the box above.

circles representing the hcp structure in the box above. Using colored pencils, pens or crayons, draw

Using colored pencils, pens or crayons, draw circles representing the ccp structure in the box above.

CHEMICAL BONDING

CRYSTAL PACKING

9 10
9
10

Here you see another packing structure in which eight atoms are located at the corners of a cube and a ninth atom is at the center of the cube. This is called body centered cubic, or bcc. Picture 9 shows a space filling model and picture 10 shows a ball and stick model.

As you can see in the table below, the metals have packing structures which are related to their places in the periodic table.

= bcc = hcp
= bcc
= hcp
related to their places in the periodic table. = bcc = hcp = ccp In the

= ccp

In the box below, you draw a bcc structure for 13 atoms.

ccp In the box below, you draw a bcc structure for 13 atoms. Using spheres, such

Using spheres, such as marbles, bbs, ping pong balls, etc. experiment with hcp, ccp and bcc pack- ing in order to determine which is the most efficient packing, i.e., which can get the most spheres into the same space.

Comparing the packing structures of the metals to their electronegativity, do you find any relationship?

Li
Li
Be
Be
Na
Na
Mg
Mg
Al
Al
 
K
K
Ca
Ca
Sc
Sc
Ti
Ti
V
V
Cr
Cr

Mn

Fe
Fe
Co
Co
Ni
Ni
Cu
Cu

GaK Ca Sc Ti V Cr Mn Fe Co Ni Cu

Rb
Rb
Sr
Sr
Y
Y
Zr
Zr
Nb
Nb
Mo
Mo
Tc
Tc
Ru
Ru
Rh
Rh
Pd
Pd
Ag
Ag

SnIn

In

Cs
Cs
Ba
Ba
Lu
Lu
Hf
Hf
Ta
Ta
W
W
Re
Re
Os
Os
Ir
Ir
Pt
Pt
Au
Au

Hg

Tl
Tl
Pb
Pb

15

ENERGY

CHEMICAL BONDING

COVALENT H 2

Hydrogen DIHYDROGEN MOLECULE Atom P o t e n t i a l E n
Hydrogen
DIHYDROGEN MOLECULE
Atom
P
o t
e
n
t
i
a l
E n e r g y

Internuclear Distance

Suppose you have two well separated hydrogen atoms and begin moving them closer together. From the picture aboveyou can see that the energy of the system will decline as they are being moved together until at some distance the system will have a minimum energy.

What causes to energy to rise as the atoms are moved closer than the minimum energy?

A dihydrogen molecule consists of two hydrogen nuclei

(protons) held a fixed distance apart and surrounded by

a probability density cloud of two electrons.

As you can see from the picture above, the separa-

tion is that at which the system is in the state of lowest energy. But what are the factors which cause this to be

a low energy state?

There are primarily two factors. They are quantum and electrostatic effects. Quantum theory produces two effects, lowered energy and discrete energy levels.

Confining electrons makes them ‘dance’. This is part of quantum theory. The tighter electrons are squeezed the harder they dance. Dancing electrons have kinetic energy. But electrons will slow down if they can. When they have more room they can slow down, which means they have less kinetic energy. In a hydrogen molecule the electrons can move through the space of two atoms instead of one, which means that they have more room and thus can dance slower and have less kinetic energy. (Picture 1) There are also electric attractions and repulsions between the particles in the molecule. Picture 2 shows the repulsions of like charges as colored arrows and the attractions of opposite charges as black arrows. The additive combination of the electric and kinetic energy effects gives the covalent bond for hydrogen.

16

1

the electric and kinetic energy effects gives the covalent bond for hydrogen. 16 1 H H
the electric and kinetic energy effects gives the covalent bond for hydrogen. 16 1 H H

H

H

the electric and kinetic energy effects gives the covalent bond for hydrogen. 16 1 H H

H 2

the electric and kinetic energy effects gives the covalent bond for hydrogen. 16 1 H H
DISTANCE � � � �
DISTANCE
� �
� �

2

CHEMICAL BONDING

QUANTIZATION

Just below we show two hydrogen atoms and their combination as H 2 on the right.

atoms and their combination as H 2 on the right. + The red electron cloud represents

+

atoms and their combination as H 2 on the right. + The red electron cloud represents

The red electron cloud represents the probable location of the electrons. Notice that the space for electrons is larger in the H 2 molecule than it is in the separated hydrogen atoms.

H 2 molecule than it is in the separated hydrogen atoms. + e e 1 11
H 2 molecule than it is in the separated hydrogen atoms. + e e 1 11
+ e e 1 11 ENERGY
+
e
e
1
11
ENERGY
is in the separated hydrogen atoms. + e e 1 11 ENERGY zero energy e e
is in the separated hydrogen atoms. + e e 1 11 ENERGY zero energy e e

zero energy

separated hydrogen atoms. + e e 1 11 ENERGY zero energy e e 2 ENERGY One
e e 2 ENERGY
e
e
2
ENERGY

One of the basic principles of quantum mechanics is that whenever anything is confined in a finite space, it can only occupy one of a discrete set of energy levels. It is also the case that when the space is made larger the energy states are lower. In picture 1 the blue lines represent the energy states available for a particle confined between the orange walls. In picture 2 the blue lines show how the energy states are lower when the particles are given more space.

Now that we know why covalent bonding occurs we will use simplified pictures known as overlapping orbitals to describe more complicated molecules. Just to the right we show this model for hydrogen.

Which picture, number 1 or number 2, has the lowest total energy?

If picture 1 represents the energy states of two separate hydrogen atoms, then what could picture 2 represent?

These pictures do not necessarily show that if you move two hydrogen atoms close together they will bond to form a hydrogen molecule but they do show that the hydrogen molecule will be at a lower energy state than the combined energies of the separate atoms and that you would need to add energy to the molecule to get the atoms separated and that therefore the molecule will hold together until you add that energy.

17

the molecule to get the atoms separated and that therefore the molecule will hold together until

+

the molecule to get the atoms separated and that therefore the molecule will hold together until

CHEMICAL BONDING

BOND LENGTH AND STRENGTH

BOND LENGTH

BOND STRENGTH

0 H H H Cl H C C C C C C C C O
0
H
H
H
Cl
H
C
C
C
C
C
C
C
C
O
C
O
C
O
N
N
N
N
N
N
F
F
1200 kJ/mol
Cl
Cl
Br
Br
900
kJ/mol
I
I
600
kJ/mol
C
F
C
Cl
300
kJ/mol
C
Br
C
I
0
50 pm
100
pm
150
pm
200
pm
250
pm
300
pm
300
pm
250
200
pm
pm
150
100
pm
pm
50 pm
300
600
kJ/mol
kJ/mol
900
kJ/mol
1200 kJ/mol

Which are the longest and shortest bonds shown? Which are the strongest and weakest bonds shown?

In each group of related compounds, what correla- tion do you observe between bond length and bond strength? What are some exceptions?

18

CHEMICAL BONDING

STRONG AND WEAK BONDS

kJ/mol 0 500 1000 1500 2000 2500 3000 3500 4000 MgO CaO MgCl 2 CaCl
kJ/mol
0
500
1000
1500
2000
2500
3000
3500
4000
MgO
CaO
MgCl
2
CaCl
2
LiF
NaF
KCl
N
N
C
C
C
C
O
O
H
F
O
H
C
H
N
H
N
C
F
F
W
Hg

kJ/mol

Ionic Lattice Energy Covalent Bond Energy Metallic Lattice Energy Intermolecular Bond Energy kJ/mol 0 5
Ionic Lattice Energy
Covalent Bond Energy
Metallic Lattice Energy
Intermolecular Bond Energy
kJ/mol
0
5
10
15
20
kJ/mol
Ion-Permanent Dipole
Hydrogen Bonding
Permanent Dipole-Permanent Dipole
H 2 O
HCl
Permanent Dipole-Induced Dipole
HCl–Ar
Induced Dipole-Induced Dipole
He

19

CHEMICAL BONDING

STRONG AND WEAK BONDS

STRONG BONDS

A. Ionic

Much of the strength of ionic bonding comes about when the ions are packed together in crystal lattices, so that each ion is held in an attractive field with several neigh- bors of the opposite charge. These binding energies can range up to several thousand kilojoules per mole.

B. Covalent

Covalent bonds are also strong, ranging up to 940 kilojoules per mole for triple bound N 2 .

C. Metallic

Metals are also strongly bonded, as you can deduce from their strength and hardness, although the liquid

metal mercury is an exception.

WEAK BONDS

Weak bonds, often called intermolecular forces, are several orders of magnitude weaker that strong bonds described above. One of the relatively stronger of the weak bonds is hydrogen bonding with energies ranging from two to ten kilojoules per mole.

D. Ion-Permanent Dipole

These would include salts dissolved in a polar sub- stance, e.g., NaCl dissolved in water.

E. Permanent Dipole - Permanent Dipole

This class of bond includes hydrogen bonding.

F. Ion - Induced Dipole

G. Permanent Dipole - Induced Dipole

H. Induced Dipole - Induced Dipole

These are also known as van der Waals forces or as London dispersion forces. They are quite weak but they always exist between nearby molecules and they are always attractive.

20

1000 kJ/mol

900 kJ/mol

800 kJ/mol

700

kJ/mol

600

kJ/mol

500

kJ/mol

400

kJ/mol

300

kJ/mol

200

kJ/mol

100

kJ/mol

10 kJ/mol

kJ/mol 400 kJ/mol 300 kJ/mol 200 kJ/mol 100 kJ/mol 10 kJ/mol A B W Hg C

A

B

W

Hg

C

kJ/mol 400 kJ/mol 300 kJ/mol 200 kJ/mol 100 kJ/mol 10 kJ/mol A B W Hg C

D, E, F, G, H

CHEMICAL BONDING

COVALENT TO METALLIC

While we have a simple gradation between ionic and covalent compounds, we are also able to find a path of bonding types which goes from covalent to metal- lic bonding. This is not a simple gradation but rather detours through the network covalent bonds, some of which are semiconductors.

Our essential procedure in tracing the connections between these types of bonding is to follow the valence electrons. In covalent bonding the bonding pairs of electrons are held in distinct orbitals, even though their physical location is, as always, given by a continuous probability density. Several atoms, both like and unlike, can be connected pair-wise together by covalent bonds and large mole- cules, particularly organic, can be constructed this way. However, we also begin to see phenomena other than pair wise bonding between definite atoms appearing. An example is ozone, O 3 , a linear molecule in which each of the outer atoms is bonded to the central atom equally, but with both of them sharing three bonds between them. In this case the individual electrons cannot be assigned to a definite bond and are said to be delocalized. There are some types of atoms, such as carbon and silicon, where covalent bonds form between unlimited numbers of the atoms. In the graphite form of carbon three of the bonding electrons of each carbon atom form covalent bonds between neighboring atoms to form a hexagonal planar structure, but the fourth bond- ing electron sticks out between planes. These bonds overlap and connect the planes together and they are also delocalized, which means that these electrons are free to move around under, say the pressure of an elec- tric field and thus graphite is an electrical conductor. Finally, in metals, all of the valence electrons are held communally by the whole substance and are thus free to conduct electricity or heat. There are also more extreme cases of delocalization than metals. These include superconductors and the new Bose-Einstein condensates.

21

Electrons can only be located in space with a probabil- ity density, but we can also locate electrons with regard to their situation with respect to other entities.

For example, there are free electrons which are not bound to any atom or molecule but are pushed about by electric and magnetic fields. On earth, they usually do not remain free very long but end up (at least for a while) in one of the following situations.

Describe the location , stability and energy level of an electron in each of the situations listed below.

An electron in an atomic orbital.

An electron in a subshell.

An electron in a shell.

A valence electron.

An electron in a filled shell.

An electron in an atom.

An electron in an excited state.

An electron in a negative ion.

An electron in a positive ion.

An electron in a molecular orbital.

A valence electron in a metal.

A valence electron in a superconductor.

An electron in a Bose-Einstein condensate.

CHEMICAL BONDING

Electrons are held by each atom in completed shells.

CsF

Ionic

1

Localized

Rb at 10 -8 KNaCl

Bonding electron pairs cluster around the most electronegative atom(s).

Polar Covalent

H 2 O

2

CO 2

CO

shared

electron

equally by

pairs are

Bonding

Covalent

O 2

3

Molecular Orbitals

Some bonding electrons are held collec- tively inside the molecule.

O 3

4

C 6 H 6

A small proportion of the electrons are free to move about the lattice.

Semiconductors

Si

5

In graphite, valence elec- trons are free to move in two dimensions.

Semi-metallic

Graphite

6

All valence electrons are free to move throughout the lattice.

ELECTRON DELOCALIZATION

Metals

Gold

7

Superconductors

All the valence electrons are free to move without resistance.

K 3 C 60 at 19K

8

In a Bose-Einstein condensate all of the electrons become part of a single ‘atom’.

Delocalized

Bose-Einstein

9

3 In a homonuclear diatomic molecule the binding electron pairs are shared evenly and symmetrically
3
In a homonuclear diatomic
molecule the binding electron
pairs are shared evenly and
symmetrically by both atoms.
6 In graphite the carbon atoms are bound in hexa- gons that are arranged in
6
In graphite the carbon
atoms are bound in hexa-
gons that are arranged in
sheets. The sheets are
loosely bound to each
other and the electrons
between the sheets are
free to move.
9 In the picture at right, the small grey dots represent the separate nuclei. The
9
In the picture at right, the
small grey dots represent
the separate nuclei. The
red cloud represents all
(not just the valence) elec-
trons held in common by
the substance, as if it were
one atom.
2 When two atoms of moder- ately different electronega- tivity are bound, the bind- ing
2
When two atoms of moder-
ately different electronega-
tivity are bound, the bind-
ing electrons are shared
unevenly, tending toward
the more electronegative
atom.
5 In a semiconductor, such as Silicon, a small minority of valence electrons are free
5
In a semiconductor, such
as Silicon, a small minority
of valence electrons are
free to move about the
lattice.
The free electron is shown
as the small red blur at
right.

8

both atoms. 1 Filled shells are shown in grey. Valence electron clouds are in red.
both atoms.
1
Filled shells are shown
in grey.
Valence electron clouds
are in red.
Negative ions are out-
lined in red.
Positive ions are out-
lined in blue.
Cl
Na
Na +
-
Cl
4 In Benzene six of the bonding electrons are held collectively by the molecule as
4
In Benzene six of the
bonding electrons are
held collectively by the
molecule as a whole. In
the picture these are rep-
resented by the red cloud.
7 In the picture at right, the gray circles represent the core of filled shells
7
In the picture at right, the
gray circles represent the
core of filled shells while
the red cloud is the set of
valence or conducting elec-
trons held in common by
the metal. Compare and
contrast with number nine.

22

is the set of valence or conducting elec- trons held in common by the metal. Compare
is the set of valence or conducting elec- trons held in common by the metal. Compare